CN107525858A - The screening method of glucocorticoid chemical risk material in a kind of washing product - Google Patents
The screening method of glucocorticoid chemical risk material in a kind of washing product Download PDFInfo
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- CN107525858A CN107525858A CN201710195127.7A CN201710195127A CN107525858A CN 107525858 A CN107525858 A CN 107525858A CN 201710195127 A CN201710195127 A CN 201710195127A CN 107525858 A CN107525858 A CN 107525858A
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Abstract
The invention discloses glucocorticoid chemical risk material screening method in a kind of washing product, comprise the following steps：(1) accurate mass database and the mass spectrum spectrum storehouse of testing compound are established；(2) pre-treatment and detection of actual sample：The pre-treatment steps such as washing product sample is extracted, centrifugation, purification, filtering, obtained sample solution carry out the analysis detection of ultrahigh pressure liquid phase chromatogram quadrupole rod electrostatic field orbit trap high resolution mass spectrum；(3) result of the test for obtaining step (2) is compared and analyzed with the accurate mass database established in step (1) and mass spectrum spectrum storehouse, carries out the examination of glucocorticoid chemical risk material.Glucocorticoid chemical risk material screening method accuracy height, high specificity, high sensitivity, are applicable to routine testing and the quality control of washing product in the washing product that the present invention establishes.
Description
Technical field
The present invention relates to a kind of screening method of chemical substance, and ultrahigh pressure liquid phase chromatogram-four is based on more particularly to one kind
The examination side of glucocorticoid chemical risk material in the washing product of pole bar-electrostatic field orbit trap high resolution mass spectrum GC-MS
Method.
Background technology
1. there is potential hazard effect in the chemical risk material in washing product to consumer's health of human body.
Washing product is exactly to pursue clean, health and fashion life for people to provide safeguard at the beginning of the birth, with society
Meeting makes constant progress, and pursuit of the people to clean, health and the life style of fashion also constantly upgrades, and shield is washed so as to drive
Articles for use industry has stepped into the fast traffic lane of development and upgrading.Currently, washing product market product is a feast for the eyes, functionalization, sectionalization,
Specialized product continues to bring out, and meets the multiple demand of consumers in general.
Today of people's daily necessities is had become in washing product, its security is also more and more in widespread attention.
2014, Han Yi shampoos were detected to contain possible carcinogenic substance acrylamide, two of which by third party authority testing agency
Preservative-methylisothiazolinone and methylchloroisothiazandnone are also detected exceeded nearly twice, easily cause human body skin mistake
It is quick；As the baby shampoo of one of the significant product of Johnson ＆ Johnson, its maximum attraction is exactly not stimulate eyes, but the product is 2009
Year finds dioxane containing noxious material by the U.S. and can discharge the quaternary ammonium salt component of formaldehyde；2010, Beijing's prevention from suffering from the diseases
During domestic washing product is spot-check, significant proportion product is detected the inspection of phthalic acid ester, wherein perfume for control centre
Extracting rate is up to 92.3% (phthalic acid ester is the environmental hormone for endangering human reproduction's ability)；In addition, three in bath accessory
Chlorine is raw and antibiotic in other washing products and hormone etc. are also potential chemical risk material.
Long-term use washing shield product and can cause that skin of face blackspot, atrophy be thinning, bone containing above-mentioned poisonous and harmful substance
Matter is loose, muscular atrophy, metabolic disorder the problems such as, can seriously cause the generation of cancer.The effect that businessman brings in short term for it,
To attract customer to buy, still using combined set system class, in certain or certain several prods added with the similar activity such as hormone into
Point, also allow for escaping inspection.Therefore, its harmfulness should not be underestimated.
2. the supervision of chemical risk material relatively lags behind in washing product, prevent scarce capacity.
Monitoring system (NEISS) statistics is injured according to American National electronics, all kinds of washing products trigger within 2001~2009 years
Security incident it is accumulative up to 7405.European Union's quick early warning system of the non-food stuff class consumer goods (RAPEX), U.S.'s Consumer Product Safety committee
Member's meeting (CPSC), food and medicine Surveillance Authority of the U.S. (FDA) have also been issued for adding chemicals in violation of rules and regulations in washing product
The Risk-warning of matter.
In recent years, China is put into terms of washing product security control financial resources, man power and material are more and more, but more
Drill in face of stronger product security incident, still seem unable to do what one wishes.Wherein subject matter is that the regulatory format in China is more with afterwards
Based on remedying, made an effort in terms of the prevention of product early stage still inadequate, it is mainly shown as that developed country puts into effect newly repeatedly
Rules and regulations, cause the product in China to be called back again and again, such as 2013, baby's washing product of Johnson ＆ Johnson is called back 48 times；It is precious
The events such as problem mouthwash were recalled in 2011 by clean (China) Co., Ltd.
3. high resolution mass spectrum has advantage in terms of the examination of chemical risk material.
At present, for the quantitative detection of target compound, domestic and international correlative study is mainly using triple quadrupole series connection matter
Spectrum.And the washing product detection method of high resolution mass spectrum technology is used to have no report.
The content of the invention
It is increasingly strict with regulation, it is desirable to which that the chemical risk amount of material of detection is more and more, passes through multiple-reaction monitoring
The conventional method that pattern is detected can not meet the requirement of this high flux examination, and the measure of chemical risk material should be to
The development of quick and high flux.Its resolution ratio of high resolution mass spectrum and Mass accuracy are substantially better than triple quadrupole mass spectrum, are that a kind of energy is same
When qualitative and quantitative mass spectrum；High-resolution can be realized in wide mass range, obtain material accurate molecular weight；Obtain real same
Position element distribution；With high sensitivity tandem mass spectrum function, the accurate mass measurement of parent ion and daughter ion is realized.Therefore, this hair
Bright technical problems to be solved, which are to provide one kind, has high-resolution and Mass accuracy, and material essence can be obtained in wide mass range
True molecular weight information, real IP is obtained, there is high sensitivity tandem mass spectrum function, realize parent ion and daughter ion
Accurate mass measurement washing product in chemical risk material screening method.
The detection method of glucocorticoid chemical risk material, comprises the following steps in a kind of washing product：
The pre-treatment and detection of sample：The pre-treatment steps such as washing product sample is extracted, centrifugation, purification, filtering, are obtained
Sample solution carry out the analysis detection of ultrahigh pressure liquid phase chromatogram-quadrupole rod-electrostatic field orbit trap high resolution mass spectrum；The super-pressure
In liquid chromatogram-quadrupole rod-electrostatic field orbit trap high resolution mass spectrum analysis detection, chromatographic separation condition is as follows：
Chromatographic column：ACQUITY UPLC BEH Shield RP18 posts, length 150mm, internal diameter 2.1mm, 1.7 μm of particle diameter；
Column temperature：40℃；Flow velocity：0.4mL min-1；Sample size：10μL.
The glucocorticoid includes fluoxyprednisolone, prednisolone, hydrocortisone, metacortandracin, cortisone, methyl and sprinkles Buddhist nun
Song Long, betamethasone, dexamethasone, flumethasone, beclomethasone, Triamcinolone acetonide, fludroxycortide, fluoxyprednisolone diacetate, sprinkle
Ni Songlong acetates, fluorometholone, hydrocortisone acetate, deflazacort, fludrocortison acetate, Prednisoni Acetas,
Cortisone acetate, methylprednisolone acetate, becort acetate, budesonide, hydrocortisone butyrate, fill in
The loose acetate of rice, fluorometholone acetate, hydrocortisone valerate, Triamcinolone acetonide acetate, fluocinonide, diflorasone
Diacetate, celestone-V, prednicarbate, Halcinonide, alclometasone double propionate, Amcinonide, clobetasol
Propionic ester, FLUTICASONE PROPIONATE, betamethasone dipropionate, BD and clobetasone butyrate.
The detection method of glucocorticoid chemical risk material in washing product of the present invention, wherein, the superelevation
In pressure liquid chromatography-quadrupole rod-electrostatic field orbit trap high resolution mass spectrum analysis detection, mobile phase and gradient elution program are shown in Table 1：
The chromatogram flow phase of table 1 and gradient elution program
In the ultrahigh pressure liquid phase chromatogram-quadrupole rod-electrostatic field orbit trap high resolution mass spectrum analysis detection, quadrupole rod-quiet
Electric field orbit trap high resolution mass spectrum testing conditions are as follows：
Electron spray voltage：Positive ion mode 3.4kV；Sheath atmospheric pressure：55, arbitrary unit；Assist gas pressure power：6, it is any single
Position；Ion source temperature：370℃；Transmit metal capillary temperature：320℃；Lens radio-frequency voltage：55V；Scanning range：Mass-to-charge ratio
100-800；First mass spectrometric full scan resolution ratio：70000, full width at half maximum (FWHM)；Orbit trap maximum capacity：1×106；Orbit trap is maximum
Injection length：80ms；
The two level daughter ion full scan resolution ratio of data dependence：17500, full width at half maximum (FWHM)；Isolate window：Mass-to-charge ratio ± 2；Return
One changes collision energy：20,40,60eV；Orbit trap maximum capacity:1×105；Orbit trap maximum injection length：80ms；Dynamic is arranged
Except the time：6s.
The detection method of glucocorticoid chemical risk material in washing product of the present invention, wherein, locate before described
Reason comprises the following steps：
0.3g washing product sample is weighed into 10mL plastic centrifuge tubes, adds 2mL saturation metabisulfite solutions, is vortexed
30s carries out mixing demulsification, then addition 4mL acetonitriles and 4mL acetonitriles, after abundant vortex 30s, ultrasonic extraction 30min；Extract solution exists
8min is centrifuged under 12000rpm rotating speeds, the supernatant after centrifugation is transferred in another 10mL plastic centrifuge tubes, adds 100mg
N- propyl group ethylenediamine SPE powder, vortex 1min, supernatant extract solution is drawn, is surpassed after 0.22 μm of filtering with microporous membrane
High pressure liquid chromatography-quadrupole rod-electrostatic field orbit trap high resolution mass spectrum analysis detection.
The screening method of glucocorticoid chemical risk material, comprises the following steps in a kind of washing product：
(1) the accurate mass database and mass spectrum spectrum storehouse, the accurate mass database for establishing testing compound include changing
The accurate mass number information of compound title, molecular formula, chromatographic retention and a precursor ion and two fragments characteristic ions,
Mass spectrum spectrum storehouse includes applying testing compound respectively caused second order mses figure after different collision energies；
(2) sample pre-treatments and detection method of the present invention；
(3) result of the test for obtaining sample pre-treatments and detection method and the accurate mass number for the testing compound established
It is compared according to storehouse and mass spectrum spectrum storehouse, only when the accurate mass number of precursor ion and two fragments characteristic ions, chromatogram
Retention time, the isotopic peak distribution of precursor ion and second order mses figure and accurate mass database and mass spectrum spectrum storehouse information are whole
During matching, it may be determined that examination detects testing compound in actual sample.
The screening method of glucocorticoid chemical risk material in washing product of the present invention, wherein, it is described to be measured
Accurate mass database and mass spectrum the spectrum storehouse method for building up of compound specifically comprise the following steps：
Accurate mass database：Compound concentration is 100 μ g/L testing compound standard liquid respectively, using superelevation hydraulic fluid
The peristaltic pump direct injected that phase chromatogram-quadrupole rod-electrostatic field orbit trap high resolution mass spectroscope is equipped with, respectively in positive and negative ion
Analysis detection is carried out under pattern, it is determined that the precursor ion accurate mass number of corresponding testing compound；
Collision energy is applied to every kind of testing compound, obtains the fragment ion of every kind of compound, selects two responses strong
The higher fragment ion of degree is as fragments characteristic ion；
In above process, it is crucial to mass spectrums such as electron spray voltage, ion source temperature, sheath atmospheric pressure, resolution ratio respectively to join
Number optimizes；
Compound concentration is the mixed standard solution of 100 μ g/L testing compound, optimizes ultrahigh pressure liquid phase chromatographic isolation bar
Part, obtain the chromatographic retention of every kind of compound；
Establish accurate mass database：Title, molecular formula, chemical abstracts numbering, the precursor of every kind of compound are inputted respectively
Accurate mass number, chromatographic retention and the retention time window of exact mass of ion number, two fragments characteristic ions, in addition also
The response lag of testing compound is inputted, when the signal response of testing compound exceedes the threshold value, corresponding precursor ion enters one
Step carries out second mass analysis；Testing compound and its precursor ion and the accurate mass number information of fragment ion are shown in Table 2；
The accurate mass number information of the testing compound of table 2 and its precursor ion and fragment ion
Establish mass spectrum spectrum storehouse：Compound concentration is 100 μ g/L testing compound standard liquid respectively, using ultrahigh pressure liquid phase
The peristaltic pump direct injection analysis that chromatogram-quadrupole rod-electrostatic field orbit trap high resolution mass spectroscope is equipped with, sets a series of differences
Collision energy, target compound is smashed to the second order mses figure for obtaining every kind of compound；Input, store all second order mses figures,
Obtain the mass spectrum spectrum storehouse of whole testing compounds.
The mass spectrogram of glucocorticoid chemical risk material is as shown in figure 1, wherein, each code name refers to relation such as in the present invention
Under：1. fluoxyprednisolone；2. prednisolone；3. hydrocortisone；4. metacortandracin；5. cortisone；6. methylprednisolone；7. times he
Meter Song；8. dexamethasone；9. flumethasone；10. beclomethasone；11. Triamcinolone acetonide；12. fludroxycortide；13. the double vinegar of fluoxyprednisolone
Acid esters；14. prednisolone acetate；15. fluorometholone；16. hydrocortisone acetate；17. deflazacort；18. fluorine hydrogen can
Loose acetate；19. Prednisoni Acetas；20. cortisone acetate；21. methylprednisolone acetate；22. betamethasone vinegar
Acid esters；23. budesonide；24. hydrocortisone butyrate；25. dexamethasone acetate；26. fluorometholone acetate；27. hydrogen
Change cortisone valerate；28. Triamcinolone acetonide acetate；29. fluocinonide；30. diflorasone diacetate；31. times he
Betamethasone valerate；32. prednicarbate；33. Halcinonide；34. alclometasone double propionate；35. Amcinonide；36. chlorine times he
Rope propionic ester；37. FLUTICASONE PROPIONATE；38. betamethasone dipropionate；39. BD；40. chlorine times he
Loose butyrate.
The screening method of glucocorticoid chemical risk material in washing product of the present invention, wherein, test compounds
Thing carries out mass spectral analysis using positive ion mode；
The preparation of standard liquid comprises the following steps：500-1000 μ g mL are prepared respectively-1Standard Stock solutions, in 4 DEG C
Under the conditions of be kept in dark place；Prepare 10 μ g mL-1Mixed standard solution, then through methanol dilution, be configured to a series of various concentrations
Matrix matching standard liquid；
The standard substance of glucocorticoid is dissolved using methanol solvate.
The screening method difference from prior art of chemical risk material is in washing product of the present invention：
The present invention is established based on ultrahigh pressure liquid phase chromatogram-quadrupole rod-electrostatic field orbit trap high resolution mass spectrum GC-MS
Washing product in glucocorticoid chemical risk material screening method, will effectively solve glucocorticoid in washing product
Technical barrier is confirmed in examination, can be used to carry out the formulation work of the risk assessment of poisonous and harmful substance and limit standard in washing product
Make, so as to reduce the occurrence probability for damaging event to consumer by chemical risk material, build consumption ring in good health
Border；Achievement in research can also guide enterprise to be avoided in process of producing product using the chemical risk material for causing potential safety hazard,
Consumer is set more clearly to recognize the potential hazard of chemical risk material in washing product, so as to improve the general safety of society
Consumption view, produce good social benefit.
The relevant laws and regulations and standard of washing product are measurement and the Main Means and technology that control product quality characteristics
Foundation, enterprise etc. have only known about these laws and regulations and standard, can just effectively facilitate the health for washing shield product and normal development,
So that product obtains good economic benefits.The screening method that the present invention establishes can provide effective technology branch for coherent detection mechanism
Support, further improve every laws and regulations on the management standard with improving washing product, the market economy rule of specification washing product industry
With management order, the capacity for technological innovation of washing product industry is improved, shortens the technological gap with international washing product industry, will
There is important economic implications to the sustainable and healthy development for accelerating Chinese relevant enterprise.
The method of the invention has high-resolution and Mass accuracy, and material accurate molecular can be obtained in wide mass range
Amount, obtains real IP, has high sensitivity tandem mass spectrum function, realize the accurate mass of parent ion and daughter ion
The screening method of chemical risk material in the washing product of measure.
The present invention establishes a kind of based on the combination of ultrahigh pressure liquid phase chromatogram-quadrupole rod-electrostatic field orbit trap high resolution mass spectrum
The rapid screening and quantitative analysis strategy of glucocorticoid in accurate mass database and the washing product in spectrum storehouse.By to this hair
Detection limit, quantitative limit, linear relationship, stability and the investigation of matrix effect and the detection of actual sample of bright method, this
Invent rapid analysis method accuracy height established, high specificity, high sensitivity, be applicable to the routine testing of washing product with
The quality of production controls.
Below in conjunction with the accompanying drawings to the present invention washing product in glucocorticoid chemical risk material screening method make into
One step explanation.
Brief description of the drawings
Fig. 1 is the mass spectrogram of glucocorticoid chemical risk material in the present invention, wherein, it is as follows that each code name refers to relation：
1. fluoxyprednisolone；2. prednisolone；3. hydrocortisone；4. metacortandracin；5. cortisone；6. methylprednisolone；7. times his rice
Pine；8. dexamethasone；9. flumethasone；10. beclomethasone；11. Triamcinolone acetonide；12. fludroxycortide；13. the double acetic acid of fluoxyprednisolone
Ester；14. prednisolone acetate；15. fluorometholone；16. hydrocortisone acetate；17. deflazacort；18. fludrocortison
Acetate；19. Prednisoni Acetas；20. cortisone acetate；21. methylprednisolone acetate；22. betamethasone acetic acid
Ester；23. budesonide；24. hydrocortisone butyrate；25. dexamethasone acetate；26. fluorometholone acetate；27. hydrogenation
Cortisone valerate；28. Triamcinolone acetonide acetate；29. fluocinonide；30. diflorasone diacetate；31. times his rice
Loose valerate；32. prednicarbate；33. Halcinonide；34. alclometasone double propionate；35. Amcinonide；36. clobetasol
Propionic ester；37. FLUTICASONE PROPIONATE；38. betamethasone dipropionate；39. BD；40. clobetasone
Butyrate.
Embodiment
Embodiment 1
The detection method of glucocorticoid chemical risk material, comprises the following steps in a kind of washing product：
Pre-treatment step, the obtained sample solutions such as washing product sample is extracted, centrifugation, purification, filtering carry out superelevation
Pressure liquid chromatography-quadrupole rod-electrostatic field orbit trap high resolution mass spectrum analysis detection；Ultrahigh pressure liquid phase chromatogram-quadrupole rod-electrostatic field
In the analysis detection of orbit trap high resolution mass spectrum, chromatographic separation condition is as follows：
Chromatographic column：ACQUITY UPLC BEH Shield RP18 posts, length 150mm, internal diameter 2.1mm, 1.7 μm of particle diameter；
Column temperature：40℃；Flow velocity：0.4mL min-1；Sample size：10 μ L, mobile phase and gradient elution program are shown in Table 1：
The chromatogram flow phase of table 1 and gradient elution program
In the ultrahigh pressure liquid phase chromatogram-quadrupole rod-electrostatic field orbit trap high resolution mass spectrum analysis detection, quadrupole rod-quiet
Electric field orbit trap high resolution mass spectrum testing conditions are as follows：
Electron spray voltage：Positive ion mode 3.4kV；Sheath atmospheric pressure：55, arbitrary unit；Assist gas pressure power：6, it is any single
Position；Ion source temperature：370℃；Transmit metal capillary temperature：320℃；Lens radio-frequency voltage：55V；Scanning range：Mass-to-charge ratio
100-800；First mass spectrometric full scan resolution ratio：70000, full width at half maximum (FWHM)；Orbit trap maximum capacity：1×106；Orbit trap is maximum
Injection length：80ms；
The two level daughter ion full scan resolution ratio of data dependence：17500, full width at half maximum (FWHM)；Isolate window：Mass-to-charge ratio ± 2；Return
One changes collision energy：20,40,60eV；Orbit trap maximum capacity:1×105；Orbit trap maximum injection length：80ms；Dynamic is arranged
Except the time：6s.
Pre-treatment comprises the following steps：
0.3g washing product sample is weighed into 10mL plastic centrifuge tubes, adds 2mL saturation metabisulfite solutions, is vortexed
30s carries out mixing demulsification, then addition 4mL acetonitriles and 4mL acetonitriles, after abundant vortex 30s, ultrasonic extraction 30min；Extract solution exists
8min is centrifuged under 12000rpm rotating speeds, the supernatant after centrifugation is transferred in another 10mL plastic centrifuge tubes, adds 100mg
N- propyl group ethylenediamine SPE powder, vortex 1min, supernatant extract solution is drawn, is surpassed after 0.22 μm of filtering with microporous membrane
High pressure liquid chromatography-quadrupole rod-electrostatic field orbit trap high resolution mass spectrum analysis detection.
The glucocorticoid includes fluoxyprednisolone, prednisolone, hydrocortisone, metacortandracin, cortisone, methyl and sprinkles Buddhist nun
Song Long, betamethasone, dexamethasone, flumethasone, beclomethasone, Triamcinolone acetonide, fludroxycortide, fluoxyprednisolone diacetate, sprinkle
Ni Songlong acetates, fluorometholone, hydrocortisone acetate, deflazacort, fludrocortison acetate, Prednisoni Acetas,
Cortisone acetate, methylprednisolone acetate, becort acetate, budesonide, hydrocortisone butyrate, fill in
The loose acetate of rice, fluorometholone acetate, hydrocortisone valerate, Triamcinolone acetonide acetate, fluocinonide, diflorasone
Diacetate, celestone-V, prednicarbate, Halcinonide, alclometasone double propionate, Amcinonide, clobetasol
Propionic ester, FLUTICASONE PROPIONATE, betamethasone dipropionate, BD and clobetasone butyrate.
Using the method for the present embodiment 1 55 washing product samples have been carried out with the inspection of glucocorticoid chemical risk material
Survey.As a result show there are 2 examinations to go out containing dexamethasone (content is respectively 127.561mg/kg and 53.463mg/kg), 1
Sample sifter is found to be found containing clobetasol propionic acid containing celestone-V (content 17.896mg/kg), 1 sample sifter
Ester (content 53.972mg/kg).
Embodiment 2
First, instrument and reagent
Rapidly and efficiently liquid chromatographic system (the Thermo Fisher companies of the U.S.) of Dionex UltiMate 3000；Q
Exactive Focus quadrupole rods-electrostatic field orbit trap high-resolution mass spectrometer (Thermo Fisher companies of the U.S.)；Milli-Q
Ultra-pure water instrument (Millipore companies of the U.S.)；The turbula shakers of Vortex-Genie 2 (U.S. Scientific
Industries companies).
Methanol, acetonitrile (chromatographically pure, Thermo Fisher companies of the U.S.)；Ammonium hydroxide, formic acid (chromatographically pure, U.S. Dima
Technology companies)；Use for laboratory water is deionized water.Carbon 18, N- propyl group ethylenediamine and ketjenblack EC (Germany
Macherey-Nagel companies)；Multi-walled carbon nanotube (German Miltenyi Biotec GmbH companies)；Anhydrous magnesium sulfate, chlorine
Change sodium (Guangzhou West Gansu Province chemical industry Co., Ltd)；0.22 μm of miillpore filter (Pall companies of the U.S.).
500-1000 μ g mL are prepared respectively-1Standard Stock solutions, be kept in dark place under the conditions of 4 DEG C.Prepare 10 μ g mL-1Mixed standard solution, then through methanol dilution, be configured to a series of matrix matching standard liquid of various concentrations.
The information such as molecular formula, molecular weight, chemical abstracts numbering, Determination of oil-water partition coefficient and the preparation solvent of target compound are shown in
Table 3.
Title, molecular formula, molecular weight, chemical abstracts numbering, Determination of oil-water partition coefficient and the preparation solvent of the target compound of table 3
Etc. information
2nd, the foundation in accurate mass database and mass spectrum spectrum storehouse
Accurate mass database include compound name, molecular formula (be used for calculate isotopic peak distribution), retention time and
The accurate mass number (table 4) of precursor ion and two fragments characteristic ions.Spectrum storehouse is included for every kind of compound using different
Through second order mses figure caused by analysis after collision energy.Spectrum storehouse can be regarded as to sampled data through accurate mass database examination
Auxiliary confirmation means afterwards.
Accurate mass database and mass spectrum the spectrum storehouse method for building up of testing compound specifically comprise the following steps：
Accurate mass database：Compound concentration is 100 μ g/L testing compound standard liquid respectively, using superelevation hydraulic fluid
The peristaltic pump direct injected that phase chromatogram-quadrupole rod-electrostatic field orbit trap high resolution mass spectroscope is equipped with, respectively in positive and negative ion
Analysis detection is carried out under pattern, it is determined that the precursor ion accurate mass number of corresponding testing compound；
Collision energy is applied to every kind of testing compound, obtains the fragment ion of every kind of compound, selects two responses strong
The higher fragment ion of degree is as fragments characteristic ion；
In above process, it is crucial to mass spectrums such as electron spray voltage, ion source temperature, sheath atmospheric pressure, resolution ratio respectively to join
Number optimizes；
Compound concentration is the mixed standard solution of 100 μ g/L testing compound, optimizes ultrahigh pressure liquid phase chromatographic isolation bar
Part, obtain the chromatographic retention of every kind of compound；
Establish accurate mass database：Title, molecular formula, chemical abstracts numbering, the precursor of every kind of compound are inputted respectively
Accurate mass number, chromatographic retention and the retention time window of exact mass of ion number, two fragments characteristic ions, in addition also
The response lag of testing compound is inputted, when the signal response of testing compound exceedes the threshold value, corresponding precursor ion enters one
Step carries out second mass analysis；
Establish mass spectrum spectrum storehouse：Compound concentration is 100 μ g/L testing compound standard liquid respectively, using ultrahigh pressure liquid phase
The peristaltic pump direct injection analysis that chromatogram-quadrupole rod-electrostatic field orbit trap high resolution mass spectroscope is equipped with, sets a series of differences
Collision energy, target compound is smashed to the second order mses figure for obtaining every kind of compound；Input, store all second order mses figures,
Obtain the mass spectrum spectrum storehouse of whole testing compounds.
The mass spectrogram of glucocorticoid chemical risk material is as shown in figure 1, wherein, each code name refers to relation such as in the present invention
Under：1. fluoxyprednisolone；2. prednisolone；3. hydrocortisone；4. metacortandracin；5. cortisone；6. methylprednisolone；7. times he
Meter Song；8. dexamethasone；9. flumethasone；10. beclomethasone；11. Triamcinolone acetonide；12. fludroxycortide；13. the double vinegar of fluoxyprednisolone
Acid esters；14. prednisolone acetate；15. fluorometholone；16. hydrocortisone acetate；17. deflazacort；18. fluorine hydrogen can
Loose acetate；19. Prednisoni Acetas；20. cortisone acetate；21. methylprednisolone acetate；22. betamethasone vinegar
Acid esters；23. budesonide；24. hydrocortisone butyrate；25. dexamethasone acetate；26. fluorometholone acetate；27. hydrogen
Change cortisone valerate；28. Triamcinolone acetonide acetate；29. fluocinonide；30. diflorasone diacetate；31. times he
Betamethasone valerate；32. prednicarbate；33. Halcinonide；34. alclometasone double propionate；35. Amcinonide；36. chlorine times he
Rope propionic ester；37. FLUTICASONE PROPIONATE；38. betamethasone dipropionate；39. BD；40. chlorine times he
Loose butyrate.
3rd, sample pre-treatments
0.3g washing product sample is weighed into 10mL plastic centrifuge tubes, adds 2mL saturation metabisulfite solutions, is vortexed
30s carries out mixing demulsification, then addition 4mL acetonitriles and 4mL acetonitriles, after abundant vortex 30s, ultrasonic extraction 30min；Extract solution exists
8min is centrifuged under 12000rpm rotating speeds, the supernatant after centrifugation is transferred in another 10mL plastic centrifuge tubes, adds 100mg
N- propyl group ethylenediamine SPE powder, vortex 1min, supernatant extract solution is drawn, is surpassed after 0.22 μm of filtering with microporous membrane
High pressure liquid chromatography-quadrupole rod-electrostatic field orbit trap high resolution mass spectrum analysis detection.
4th, chromatographic separation condition
Chromatographic column：ACQUITY UPLC BEH Shield RP18 posts, length 150mm, internal diameter 2.1mm, 1.7 μm of particle diameter；
Column temperature：40℃；Flow velocity：0.4mL min-1；Sample size：10 μ L, mobile phase and gradient elution program are shown in Table 1：
The chromatogram flow phase of table 1 and gradient elution program
5th, Mass Spectrometer Method condition
Electron spray voltage：Positive ion mode 3.4kV；Sheath atmospheric pressure：55, arbitrary unit；Assist gas pressure power：6, it is any single
Position；Ion source temperature：370℃；Transmit metal capillary temperature：320℃；Lens radio-frequency voltage：55V；Scanning range：Mass-to-charge ratio
100-800；First mass spectrometric full scan resolution ratio：70000, full width at half maximum (FWHM)；Orbit trap maximum capacity：1×106；Orbit trap is maximum
Injection length：80ms；
The two level daughter ion full scan resolution ratio of data dependence：17500, full width at half maximum (FWHM)；Isolate window：Mass-to-charge ratio ± 2；Return
One changes collision energy：20,40,60eV；Orbit trap maximum capacity:1×105；Orbit trap maximum injection length：80ms；Dynamic is arranged
Except the time：6s.
6th, experimental data compares analysis
Accurate mass database and mass spectrum the spectrum storehouse of sample detection experimental data and the testing compound of foundation are entered
Row compares analysis, only when the accurate mass number of precursor ion and two fragments characteristic ions, chromatographic retention, precursor ion
Isotopic peak distribution and second order mses figure and accurate mass database and mass spectrum compose when all being matched in storehouse, be as a result just shown as
Positive.
Specifically comprise the following steps：
Mass number is set to extract window, retention time window and IP threshold parameter, according to set parameter,
The sample data gathered is compared：
First, it is not less than 1 × 10 according to the parameter of setting, such as mass number extraction window ± 5ppm, chromatographic peak area6, enter
The extraction of precursor ion accurate mass number in row database；If there is targeted in database in sample full scan gathered data
The precursor ion mass number of compound, and chromatographic peak area is not less than 1 × 106, then be considered as precursor ion accurate mass number compare into
Work(；
Second, chromatographic retention, the retention time window standard deviation of setting is ± 3, if the chromatogram of precursor ion
Retention time falls in database in the range of corresponding retention time standard deviation ± 3, then being considered as retention time, the match is successful；
3rd, IP calculating is carried out according to the molecular formula of testing compound, the threshold value of setting is 90%, works as sample
The IP of precursor ion and database compare matching degree 90% in data, then are considered as that the match is successful；
4th, two fragment ions that two fragments characteristic ions in database obtain with experimental result collection
Comparison situation, if fragment ion accurate mass number deviation is no more than ± 5ppm in experiment value and database, be considered as matching into
Work(；
5th, the second order mses figure for testing collection acquisition is compared with mass spectrum spectrum storehouse；At this stage, precursor ion,
Whole fragment ion and relative ion abundance ratios are compared, if all coincide, are considered as that the match is successful.
7th, result
Using the method for the present embodiment 2 55 washing product samples have been carried out with the inspection of glucocorticoid chemical risk material
Survey.As a result show there are 2 examinations to go out containing dexamethasone (content is respectively 127.561mg/kg and 53.463mg/kg), 1
Sample sifter is found to be found containing clobetasol propionic acid containing celestone-V (content 17.896mg/kg), 1 sample sifter
Ester (content 53.972mg/kg).
8th, discuss
1st, the foundation of screening method
To give full play to advantage of the electrostatic field orbit trap high resolution mass spectrum in Screening analysis, this research using full scan-
The two level daughter ion scan mode of data dependence.In this acquisition mode, mass spectrum carries out total quality number (m/z 100- first
800) scan, when the ion of some target compounds in database is detected and its intensity is not less than a certain given threshold,
Then the ion, which will be admitted in energetic encounter pond, carries out fragmentation, and produces daughter fragment ion.
In the compound examination stage, the three big key parameter of detection Main Basiss of target substance：Precursor ion accurate mass
Number, retention time and isotopic peak distribution.Detection sensitivity and selection of the setting of accurate mass number extraction window for method
Property has vital influence.In the present invention, it is 100 μ g L that concentration, which has been respectively adopted,-1Mixed standard solution and 500 μ g
kg-1Mark-on sample carry out the optimization of this parameter.Test result indicates that in two kinds of solution, mass number deviation is better than respectively
2ppm and 3.5ppm.Confirmed in view of follow-up fragments characteristic ion and two level spectrogram, while also avoid false negative result as far as possible
Appearance, originally grind and the extraction window of mass number be arranged to 5ppm, now both can guarantee that the appearance of no false negative result, and other side
The selectivity of method detection and sensitivity do not make significant difference.For retention time parameter, the reasonable setting of retention time window for
The accuracy of screening results plays more important effect.Due to different high resolution mass spectrum systematic differences and the behaviour of different personnel
Make, retention time may have gentle drift, and therefore, this research equipment retention time window is Average residence time ± 3
× retention time standard deviation.In the mass spectrum full scan stage, because the setting of different resolution is to the selectivity of method and sensitive
There is also certain influence, this research also to have carried out detailed optimization to mass resolution parameter for degree.Three differences of Setup Experiments
Resolution ratio (30000,50000,70000 full width at half maximum (FWHM)) carry out data acquisition respectively, the results showed that, in 70000 fulls width at half maximum (FWHM)
Resolution ratio under, the Mass accuracy highest of all target compounds, sensitivity, without significant difference, and stills provide compared with the above two
10~15 scanning element is to obtain excellent chromatographic peak profile.
In the confirmation stage, this research acquires the second order mses figure of each target compound, and have recorded every kind of compound
Two fragments characteristic exact mass of ion numbers.In first mass spectrometric sweep phase, the resolution ratio of 70000 fulls width at half maximum (FWHM) provides enough
High selectivity, now, sensitivity should be the main aspects considered, and therefore, in the confirmation stage, we set mass resolution
For 17500 relatively low and conventional fulls width at half maximum (FWHM).To obtain more complete second order mses figure, this research employs normalization impact energy
20,40 and 60eV is measured, and records the accurate mass number of the higher fragment ion of two of which response intensity into database.In high score
Distinguish in mass spectral analysis, for some key parameters, such as spray voltage, capillary temperature, gas curtain gas, purge gass and lens radio frequency
Voltage has also carried out detailed optimization.
2nd, the optimization of sample extraction and purification method
The present invention uses the sample extraction mode of ultrasound assisted extraction.First, to conventional organic solvent methanol, acetonitrile with
And the isometric ratio mixed solvent methanol+acetonitrile (1 of the two:1, v/v) investigation of rate of recovery effect has been carried out.In view of solvent
To the efficient and harmonious of all target compounds extraction, methanol+acetonitrile (1 is chosen in this research first:1, v/v) it is molten as extracting
Agent.
When only using solvent extraction, when extract solution crosses upper machine analysis after miillpore filter, the matrix in washing product still can be to mesh
There is larger matrix interference in the analysis of mark compound, therefore, for further purification sample extracting solution, the present invention takes relatively simple
And efficient sample purification mode-dispersive solid-phase extraction.As a result show, clean-up effect of the 100mgN- propyl group ethylenediamine to sample
Preferably.Therefore, cleanser of the present invention selection 100mg N- propyl group ethylenediamines as sample.
3rd, linear relationship, detection limit and quantitative limit
Hybrid standard stock solution is diluted to the hybrid working of series concentration gradient successively with treated sample solution
Solution, it is measured under the conditions of the chromatographic mass spectrometry of optimization, with the molecular ion peak area (y) of each target substance to concentration (x)
Linearly investigated, the range of linearity, detection limit and the quantitative limit result table 5 of target compound.The linear regression of target compound
Coefficient is all higher than 0.99, shows that the linear relationship of method is good, can carry out accurate quantification.Respectively with 3 times and 10 times of signal to noise ratio
The detection limit and quantitative limit of target compound are calculated, as a result such as table 5.
Embodiment described above is only that the preferred embodiment of the present invention is described, not to the model of the present invention
Enclose and be defined, on the premise of design spirit of the present invention is not departed from, technical side of the those of ordinary skill in the art to the present invention
The various modifications and improvement that case is made, it all should fall into the protection domain of claims of the present invention determination.
Claims (7)
- A kind of 1. detection method of glucocorticoid chemical risk material in washing product, it is characterised in that：Comprise the following steps：Sample pre-treatments and detection method：Washing product sample is extracted, centrifuges, purifies, filtering pre-treatment step, obtained sample Product solution carries out the analysis detection of ultrahigh pressure liquid phase chromatogram-quadrupole rod-electrostatic field orbit trap high resolution mass spectrum；The ultrahigh pressure liquid phase In chromatogram-quadrupole rod-electrostatic field orbit trap high resolution mass spectrum analysis detection, ultrahigh pressure liquid phase chromatographic separation condition is as follows：Chromatographic column：ACQUITY UPLC BEH Shield RP18 posts, length 150mm, internal diameter 2.1mm, 1.7 μm of particle diameter；Column temperature： 40℃；Flow velocity：0.4mL min-1；Sample size：10μL；The glucocorticoid includes fluoxyprednisolone, prednisolone, hydrocortisone, metacortandracin, cortisone, Methyllprednisolone Dragon, betamethasone, dexamethasone, flumethasone, beclomethasone, Triamcinolone acetonide, fludroxycortide, fluoxyprednisolone diacetate, bold and vigorous Buddhist nun The imperial acetate of pine, fluorometholone, hydrocortisone acetate, deflazacort, fludrocortison acetate, Prednisoni Acetas, can Loose acetate, methylprednisolone acetate, becort acetate, budesonide, hydrocortisone butyrate, fill in rice Loose acetate, fluorometholone acetate, hydrocortisone valerate, Triamcinolone acetonide acetate, fluocinonide, diflorasone are double Acetate, celestone-V, prednicarbate, Halcinonide, alclometasone double propionate, Amcinonide, clobetasol third Acid esters, FLUTICASONE PROPIONATE, betamethasone dipropionate, BD and clobetasone butyrate.
- 2. the detection method of glucocorticoid chemical risk material, its feature exist in washing product according to claim 1 In：In the ultrahigh pressure liquid phase chromatogram-quadrupole rod-electrostatic field orbit trap high resolution mass spectrum analysis detection, mobile phase and gradient are washed De- program is shown in Table 1：The chromatogram flow phase of table 1 and gradient elution programIn the ultrahigh pressure liquid phase chromatogram-quadrupole rod-electrostatic field orbit trap high resolution mass spectrum analysis detection, quadrupole rod-electrostatic field Orbit trap high resolution mass spectrum testing conditions are as follows：Electron spray voltage：Positive ion mode 3.4kV；Sheath atmospheric pressure：55, arbitrary unit；Assist gas pressure power：6, arbitrary unit；From Source temperature：370℃；Transmit metal capillary temperature：320℃；Lens radio-frequency voltage：55V；Scanning range：Mass-to-charge ratio 100- 800；First mass spectrometric full scan resolution ratio：70000, full width at half maximum (FWHM)；Orbit trap maximum capacity：1×106；The maximum injection of orbit trap Time：80ms；The two level daughter ion full scan resolution ratio of data dependence：17500, full width at half maximum (FWHM)；Isolate window：Mass-to-charge ratio ± 2；Normalization Collision energy：20,40,60eV；Orbit trap maximum capacity:1×105；Orbit trap maximum injection length：80ms；When dynamic excludes Between：6s.
- 3. the detection method of glucocorticoid chemical risk material, its feature exist in washing product according to claim 1 In：The pre-treatment comprises the following steps：0.3g washing product sample is weighed into 10mL plastic centrifuge tubes, adds 2mL saturation metabisulfite solutions, vortex 30s enters Row mixing is demulsified, then addition 4mL acetonitriles and 4mL acetonitriles, after abundant vortex 30s, ultrasonic extraction 30min；Extract solution exists 8min is centrifuged under 12000rpm rotating speeds, the supernatant after centrifugation is transferred in another 10mL plastic centrifuge tubes, adds 100mg N- propyl group ethylenediamine SPE powder, vortex 1min, supernatant extract solution is drawn, is surpassed after 0.22 μm of filtering with microporous membrane High pressure liquid chromatography-quadrupole rod-electrostatic field orbit trap high resolution mass spectrum analysis detection.
- A kind of 4. screening method of glucocorticoid chemical risk material in washing product, it is characterised in that：Comprise the following steps：(1) the accurate mass database and mass spectrum spectrum storehouse, the accurate mass database for establishing testing compound include compound The accurate mass number information of title, molecular formula, chromatographic retention and a precursor ion and two fragments characteristic ions, it is described Mass spectrum spectrum storehouse includes applying testing compound respectively caused second order mses figure after different collision energies；(2) sample pre-treatments and detection method described in claim 1；(3) result of the test for obtaining sample pre-treatments and detection method and the accurate mass database for the testing compound established It is compared with mass spectrum spectrum storehouse, only when the accurate mass number of precursor ion and two fragments characteristic ions, chromatogram retain Time, the isotopic peak distribution of precursor ion and second order mses figure all match with accurate mass database and mass spectrum spectrum storehouse information When, determine that examination detects testing compound in actual sample.
- 5. the screening method of chemical risk material in washing product according to claim 4, it is characterised in that：It is described accurate Quality database and mass spectrum spectrum storehouse method for building up specifically comprise the following steps：Accurate mass database：Compound concentration is 100 μ g/L testing compound standard liquid respectively, using ultrahigh pressure liquid phase color The peristaltic pump direct injected that spectrum-quadrupole rod-electrostatic field orbit trap high resolution mass spectroscope is equipped with, respectively in positive and negative ion pattern Under carry out analysis detection, it is determined that the precursor ion accurate mass number of corresponding testing compound；Collision energy is applied to every kind of testing compound, obtains the fragment ion of every kind of compound, select two response intensities compared with High fragment ion is as fragments characteristic ion；In above process, the mass spectrum key parameters such as electron spray voltage, ion source temperature, sheath atmospheric pressure, resolution ratio are entered respectively Row optimization；Compound concentration is the mixed standard solution of 100 μ g/L testing compound, optimizes ultrahigh pressure liquid phase chromatographic separation condition, obtains To the chromatographic retention of every kind of compound；Establish accurate mass database：Title, molecular formula, chemical abstracts numbering, the precursor ion of every kind of compound are inputted respectively Accurate mass number, chromatographic retention and the retention time window of accurate mass number, two fragments characteristic ions, are also inputted in addition The response lag of testing compound, when the signal response of testing compound exceedes the threshold value, corresponding precursor ion is further entered Row second mass analysis；Testing compound and its precursor ion and the accurate mass number information of fragment ion are shown in Table 2；The accurate mass number information of the testing compound of table 2 and its precursor ion and fragment ionEstablish mass spectrum spectrum storehouse：Compound concentration is 100 μ g/L testing compound standard liquid respectively, using ultrahigh pressure liquid phase color The peristaltic pump direct injection analysis that spectrum-quadrupole rod-electrostatic field orbit trap high resolution mass spectroscope is equipped with, sets a series of differences to touch Energy is hit, target compound is smashed to the second order mses figure for obtaining every kind of compound；Input, store all second order mses figures, i.e., Obtain the mass spectrum spectrum storehouse of whole testing compounds.
- 6. the screening method of glucocorticoid chemical risk material, its feature exist in washing product according to claim 5 In：What is be compared comprises the following steps that：Mass number is set to extract window, retention time window and IP threshold parameter, according to set parameter, to institute The sample data of collection is compared：First, it is not less than 1 × 10 according to the parameter of setting, such as mass number extraction window ± 5ppm, chromatographic peak area6, carry out data The extraction of precursor ion accurate mass number in storehouse；If there is target compound in database in sample full scan gathered data Precursor ion mass number, and chromatographic peak area is not less than 1 × 106, then it is considered as precursor ion accurate mass number and compares successfully；Second, chromatographic retention, the retention time window standard deviation of setting is ± 3, if the chromatogram of precursor ion retains Time falls in database in the range of corresponding retention time standard deviation ± 3, then being considered as retention time, the match is successful；3rd, IP calculating is carried out according to the molecular formula of testing compound, the threshold value of setting is 90%, works as sample data The IP of middle precursor ion compares matching degree 90% with database, then is considered as that the match is successful；4th, the comparison for two fragment ions that two fragments characteristic ions in database obtain with experimental result collection Situation, if fragment ion accurate mass number deviation is no more than ± 5ppm in experiment value and database, it is considered as that the match is successful；5th, the second order mses figure for testing collection acquisition is compared with mass spectrum spectrum storehouse；At this stage, precursor ion, whole Fragment ion and relative ion abundance ratio are compared, if all coincide, are considered as that the match is successful.
- 7. the screening method of glucocorticoid chemical risk material, its feature exist in washing product according to claim 6 In：Testing compound carries out mass spectral analysis using positive ion mode；The preparation of standard liquid comprises the following steps：500-1000 μ g mL are prepared respectively-1Standard Stock solutions, in 4 DEG C of conditions Under be kept in dark place；Prepare 10 μ g mL-1Mixed standard solution, then through methanol dilution, be configured to a series of base of various concentrations Matter matches standard liquid；The standard substance of glucocorticoid is dissolved using methanol solvate.
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